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CN103168827B - Method for preparing freshness-retaining film through Maillard reaction of collagen and chitosan - Google Patents

Method for preparing freshness-retaining film through Maillard reaction of collagen and chitosan Download PDF

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CN103168827B
CN103168827B CN201310109321.0A CN201310109321A CN103168827B CN 103168827 B CN103168827 B CN 103168827B CN 201310109321 A CN201310109321 A CN 201310109321A CN 103168827 B CN103168827 B CN 103168827B
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maillard reaction
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fish
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CN103168827A (en
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刘永
韦寿莲
廖妙婵
刘会松
陈洁静
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Zhaoqing University
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Abstract

The invention belongs to the technical field of food freshness-retaining processing and provides a method for preparing a freshness-retaining film through Maillard reaction of collagen and chitosan. The method comprises the following steps of: (1), dissolving the collagen and chitosan in an acid aqueous solution, and carrying out reflux reaction in a round-bottom flask to obtain a Maillard reaction product; and (2), cooling the Maillard reaction product to 20 DEG C to 25 DEG C, adding glycerol to the Maillard reaction product for uniformly stirring, and removing air bubbles by ultrasonically treating for 3 minutes to 8 minutes to obtain the freshness-retaining film. The freshness-retaining film prepared by the method disclosed by the invention is safe, healthy, edible and is capable of forming a film layer on the surface of fish and meat to keep the meat fresh and remarkably prolong the shelf life of the meat and fish after being coated on the fish and meat. Besides, the method is simple to operate, easy to control, strong in operability and suitable for industrial production.

Description

胶原蛋白与壳聚糖通过美拉德反应制备保鲜涂膜的方法Collagen and chitosan prepare method for fresh-keeping coating film through Maillard reaction

技术领域 technical field

本发明属于食品保鲜加工技术领域,涉及一种制备保鲜涂膜的方法,具体涉及胶原蛋白与壳聚糖通过美拉德反应制备保鲜涂膜的方法。 The invention belongs to the technical field of food fresh-keeping processing, and relates to a method for preparing a fresh-keeping coating film, in particular to a method for preparing a fresh-keeping coating film through Maillard reaction of collagen and chitosan.

背景技术 Background technique

肉类食品是人体所需优质蛋白质的主要来源,更是人们日常生活中不可少的食品。目前,我国肉类消费主要有热鲜肉、冷冻肉和冷却肉三种。热鲜肉存在污染严重、安全卫生等问题;冷冻肉因其风味和营养受冻结和解冻影响较大,已越来越不受消费者的欢迎;冷却肉经历了自然解僵成熟的过程,质地柔软有弹性,与热鲜肉、冷冻肉相比,冷却肉具有安全卫生、滋味鲜美、口感细腻和营养价值较高等优点。随着人们生活水平的提高,冷却肉将深受消费者的欢迎,是以后生鲜肉发展的必然趋势。但是,冷却肉富含脂肪与蛋白质,易被微生物利用而产生腐败,造成货架期短而成为限制其快速发展的主要瓶颈。 Meat food is the main source of high-quality protein needed by the human body, and it is an indispensable food in people's daily life. At present, my country's meat consumption mainly includes hot fresh meat, frozen meat and chilled meat. Hot fresh meat has problems such as serious pollution, safety and hygiene; frozen meat is less and less popular with consumers because its flavor and nutrition are greatly affected by freezing and thawing; chilled meat has undergone a process of natural defrosting and maturation, and its texture Soft and elastic, compared with hot fresh meat and frozen meat, chilled meat has the advantages of safety and hygiene, delicious taste, delicate taste and high nutritional value. With the improvement of people's living standards, chilled meat will be welcomed by consumers, which is an inevitable trend in the development of fresh meat in the future. However, chilled meat is rich in fat and protein, which is easily used by microorganisms to cause spoilage, resulting in a short shelf life and becoming the main bottleneck restricting its rapid development.

近年来,保鲜涂膜因具有环保、无毒、成本低、操作简单等优点,发展较为迅速。保鲜涂膜一般是以可食性物质为原料,添加或者不添加抗菌剂,通过不同分子间相互作用形成的具有多孔网状结构的薄膜,达到抑制物质交换及阻碍微生物侵害的作用,从而防止食品腐败变质,可解决冷却肉货架期短的问题。研究者做了一些有益的研究,例如:潘思轶等采用魔芋精粉涂膜保鲜冷却猪肉(潘思轶等, 食品科学, 2004, 25(8): 177-180);姜绍通等采用茶多酚、大蒜素与天然可食性膜溶液研制成涂膜保鲜剂进行冷却猪肉的涂膜保鲜研究,通过正交试验筛选出延长冷却肉保鲜期的最佳工艺(姜绍通等, 食品科学, 2010, 31(10): 313-316);杨胜平等采用壳聚糖结合茶多酚涂膜保鲜冷却带鱼(杨胜平等, 江苏农业学报, 2010, 26(4): 818-821);辛美丽等采用壳聚糖涂膜结合低温对脆肉鲩鱼片进行效果研究(辛美丽等, 食品工业科技, 2012, 33(9): 398-401)。 In recent years, due to the advantages of environmental protection, non-toxicity, low cost, and simple operation, fresh-keeping coatings have developed rapidly. Fresh-keeping coatings are generally made of edible substances as raw materials, with or without adding antibacterial agents, and form a film with a porous network structure through the interaction between different molecules to inhibit material exchange and hinder microbial invasion, thereby preventing food spoilage Deterioration can solve the problem of short shelf life of chilled meat. Researchers have done some useful research, for example: Pan Siyi et al. use konjac powder coating to keep fresh and cool pork (Pan Siyi et al., Food Science, 2004, 25(8): 177-180); Jiang Shaotong et al. Phenol, allicin and natural edible film solution were developed into film-coated preservatives to study the film-preservation of chilled pork, and the best process for prolonging the fresh-keeping period of chilled meat was screened out through orthogonal experiments (Jiang Shaotong et al., Food Science, 2010, 31 (10): 313-316); Yang Shengping used chitosan combined with tea polyphenol coating to keep fresh and cool hairtail (Yang Shengping, Jiangsu Agricultural Journal, 2010, 26 (4): 818-821); Xin Meili et al. Research on the effect of chitosan coating combined with low temperature on crispy grass carp fillets (Xin Meili et al., Science and Technology of Food Industry, 2012, 33(9): 398-401).

大量研究表明:美拉德反应产物具有抗氧化、抗诱变、抗病毒、抗增殖、抗肿瘤等功能特性,特别是抗氧化活性,具有取代传统合成抗氧化剂的潜力。美拉德反应又称非酶促褐变,主要发生于还原糖、醛类物质以及烯酮类物质的羟基基团和氨基酸、肽类物质、蛋白质以及任何含氮化合物的氨基基团之间。目前,研究较多的是美拉德反应产物中的活性成分、抗氧化机理、抗氧化活性的影响因素。例如:章银良等评价了由酪蛋白-木糖体系产生的美拉德反应产物的抗氧化活性(章银良等, 食品科技, 2012, 37(7): 65-70);张曦等探讨了乳清蛋白-木糖美拉德反应产物的成膜性及其膜包裹对核桃仁脂质过氧化的抑制作用(张曦等, 食品科学, 2011, 32(5): 58-64);于彭伟等探讨了木糖-甘氨酸美拉德反应产物对猪肉的保鲜效果(于彭伟等, 食品科学, 2012, 33(20): 334-338)。 A large number of studies have shown that: Maillard reaction products have functional properties such as anti-oxidation, anti-mutagenesis, anti-virus, anti-proliferation, and anti-tumor, especially anti-oxidation activity, and have the potential to replace traditional synthetic antioxidants. Maillard reaction, also known as non-enzymatic browning, mainly occurs between the hydroxyl groups of reducing sugars, aldehydes, and enones and the amino groups of amino acids, peptides, proteins, and any nitrogen-containing compounds. At present, there are more researches on the active ingredients in the Maillard reaction products, the mechanism of antioxidant, and the influencing factors of antioxidant activity. For example: Zhang Yinliang et al. evaluated the antioxidant activity of Maillard reaction products produced by the casein-xylose system (Zhang Yinliang et al., Food Science and Technology, 2012, 37(7): 65-70); Zhang Xi et al. discussed whey Film-forming properties of protein-xylose Maillard reaction products and their membrane-encapsulated inhibitory effect on walnut kernel lipid peroxidation (Zhang Xi et al., Food Science, 2011, 32(5): 58-64); Yu Pengwei et al. discussed the fresh-keeping effect of xylose-glycine Maillard reaction products on pork (Yu Pengwei et al., Food Science, 2012, 33(20): 334-338).

发明内容 Contents of the invention

本发明目的在于提供一种胶原蛋白与壳聚糖通过美拉德反应制备保鲜涂膜的方法。 The purpose of the present invention is to provide a method for preparing a fresh-keeping coating film through Maillard reaction of collagen and chitosan.

本发明所述的一种胶原蛋白与壳聚糖通过美拉德反应制备保鲜涂膜的方法,其包括以下步骤:(1)将胶原蛋白与壳聚糖溶于酸性水溶液中,在圆底烧瓶中回流反应得到美拉德反应产物;(2)将上述美拉德反应产物冷却到20-25℃,加入甘油搅拌均匀,超声3-8分钟脱除气泡,得所述的保鲜涂膜。 A kind of collagen protein and chitosan of the present invention prepare the method for fresh-keeping coating film by Maillard reaction, it comprises the following steps: (1) collagen protein and chitosan are dissolved in acidic aqueous solution, in round bottom flask Medium reflux reaction to obtain the Maillard reaction product; (2) Cool the above-mentioned Maillard reaction product to 20-25°C, add glycerin and stir evenly, and remove air bubbles by ultrasonication for 3-8 minutes to obtain the fresh-keeping coating film.

根据本发明所述的制备方法的进一步特征,所述步骤(1)中,所述溶解胶原蛋白与壳聚糖的酸性水溶液的pH为4.0~6.0。 According to a further feature of the preparation method of the present invention, in the step (1), the pH of the acidic aqueous solution of dissolving collagen and chitosan is 4.0-6.0.

根据本发明所述的制备方法的进一步特征,所述步骤(1)中,胶原蛋白的浓度为0.006~0.02g/mL。 According to a further feature of the preparation method of the present invention, in the step (1), the concentration of collagen is 0.006-0.02 g/mL.

根据本发明所述的制备方法的进一步特征,所述步骤(1)中,壳聚糖的浓度为0.006~0.02g/mL。 According to a further feature of the preparation method of the present invention, in the step (1), the concentration of chitosan is 0.006-0.02 g/mL.

根据本发明所述的制备方法的进一步特征,所述步骤(1)中,回流反应温度为80~100℃。 According to a further feature of the preparation method of the present invention, in the step (1), the reflux reaction temperature is 80-100°C.

根据本发明所述的制备方法的进一步特征,所述步骤(1)中,回流反应时间为8~10小时。 According to a further feature of the preparation method of the present invention, in the step (1), the reflux reaction time is 8-10 hours.

根据本发明所述的制备方法的进一步特征,所述步骤(2)中,甘油用量为6~10mL/100mL。 According to a further feature of the preparation method of the present invention, in the step (2), the dosage of glycerol is 6-10mL/100mL.

本发明的另一目的在于提供所述的保鲜涂膜的用于鱼肉保鲜的方法。所述的方法是:将鱼肉放入所述的保鲜涂膜中浸渍,沥干,在鱼肉的表面形成一层保鲜薄膜。 Another object of the present invention is to provide a fresh-keeping method for fish using the fresh-keeping coating. The method is as follows: the fish meat is dipped in the fresh-keeping coating film, drained, and a layer of fresh-keeping film is formed on the surface of the fish meat.

与现有技术相比较,本发明具有以下有益效果: Compared with the prior art, the present invention has the following beneficial effects:

(1)本发明采用的胶原蛋白与壳聚糖具有独特的分子结构与巨大分子间交联的作用,它们具有优良的成膜性能;壳聚糖具有抗菌性,与胶原蛋白进行美拉德反应得到的产物具有抗氧化性;因此,胶原蛋白与壳聚糖通过美拉德反应产物既具有优良的成膜性能,又具有抗菌性与抗氧化性,其应用于涂膜保鲜具有极大的潜力。 (1) The collagen and chitosan adopted in the present invention have a unique molecular structure and the effect of cross-linking between huge molecules, and they have excellent film-forming properties; chitosan has antibacterial properties, and carries out Maillard reaction with collagen The obtained product has antioxidant properties; therefore, the Maillard reaction product of collagen and chitosan not only has excellent film-forming properties, but also has antibacterial and anti-oxidative properties, and its application in coating film preservation has great potential .

(2)本发明所述的保鲜涂膜安全、健康、可食,用于鱼肉涂膜后,能在其表面形成一层薄膜,起到抑制内外气体、水分和溶质交换以及阻碍微生物的侵害作用,保持肉质新鲜度,显著延长其货架期。 (2) The fresh-keeping coating film of the present invention is safe, healthy and edible. After it is used as a coating film on fish meat, a thin film can be formed on its surface, which can inhibit the exchange of internal and external gas, water and solute and hinder the invasion of microorganisms. , maintain the freshness of the meat and significantly extend its shelf life.

(3)本发明操作简单,易于控制,可操作性强,适于工业化生产。 (3) The present invention is simple in operation, easy to control, strong in operability, and suitable for industrial production.

具体实施方式 Detailed ways

下面通过具体实施例对本发明做进一步的说明,但本发明不限制于这些实施例。 The present invention will be further described below through specific examples, but the present invention is not limited to these examples.

本发明以挥发性盐基氮(TVB-N)、菌落总数(TVC)、硫代巴比妥酸值(TBA)和pH值为指标综合评价本发明的保鲜效果。 The present invention comprehensively evaluates the fresh-keeping effect of the present invention by using volatile basic nitrogen (TVB-N), total bacterial colony (TVC), thiobarbituric acid value (TBA) and pH value as indicators.

通常,当挥发性盐基氮(TVB-N)小于20mg/100g、菌落总数(TVC)小于106 CFU/g、硫代巴比妥酸值(TBA)小于2.0mg/kg以及pH小于7.0时,鱼肉均可食用。 Usually, when the volatile basic nitrogen (TVB-N) is less than 20mg/100g, the total bacterial colony (TVC) is less than 10 6 CFU/g, the thiobarbituric acid value (TBA) is less than 2.0mg/kg and the pH is less than 7.0 , fish can be eaten.

挥发性盐基氮(TVB-N)的测定:按GB/T 5009.44-2003的方法。 Determination of volatile basic nitrogen (TVB-N): according to the method of GB/T 5009.44-2003.

菌落总数(TVC)的测定:按GB 4789.2-2010的方法。 Determination of total bacterial colony (TVC): According to the method of GB 4789.2-2010.

硫代巴比妥酸值(TBA)的测定:按文献(荣建华等, 食品科技, 2012, 37(4): 115-118)的方法。 Determination of thiobarbituric acid value (TBA): according to the method in the literature (Rong Jianhua et al., Food Science and Technology, 2012, 37(4): 115-118).

实施例1 Example 1

(1)保鲜涂膜的制备:用天平分别称取0.6g胶原蛋白和2.0g壳聚糖溶解于100mL的pH 6.0水溶液中,混合均匀后将混合液在圆底烧瓶中于100℃回流反应10小时得到美拉德反应产物。将美拉德反应产物倒入烧杯中,冷却到室温,加入10mL甘油搅拌均匀,超声3分钟脱除气泡,得保鲜涂膜。 (1) Preparation of fresh-keeping coating film: Weigh 0.6g collagen and 2.0g chitosan with a balance and dissolve them in 100mL of pH 6.0 aqueous solution. hours to obtain the Maillard reaction product. Pour the Maillard reaction product into a beaker, cool to room temperature, add 10 mL of glycerin, stir evenly, and ultrasonically remove air bubbles for 3 minutes to obtain a fresh-keeping coating.

(2)实施涂膜:将鲜活罗非鱼去鳞,去内脏,洗干净,切片,放入上述保鲜涂膜浸渍2分钟,取出沥干1分钟,这时鱼片表面形成一层保鲜薄膜。 (2) Coating: remove the scales and viscera of the fresh tilapia, wash it, slice it, put it in the above-mentioned fresh-keeping coating film for 2 minutes, take it out and drain it for 1 minute, at this time a layer of fresh-keeping film is formed on the surface of the fish fillet .

(3)冷藏处理:取冷却到室温的已高温高压灭菌的培养皿两个,一大一小,将上述涂好膜的鱼片放入小的培养皿中,再用大的培养皿将小的盖好,一起放入4℃的冰箱中冷藏。 (3) Refrigeration treatment: Take two high-temperature and high-pressure sterilized petri dishes that have been cooled to room temperature, one large and one small, put the above-mentioned fish fillets coated with the film into the small petri dishes, and then use the large petri dish Cover the small ones and put them together in the refrigerator at 4°C.

(4)测定结果:上述涂膜鱼片冷藏18天后取出测定相关指标,其挥发性盐基氮(TVB-N)为16.86mg/100g,菌落总数(TVC)为105.63 CFU/g,硫代巴比妥酸值(TBA)为0.63mg/kg,pH为6.78,鱼片还具有较高的食用价值。 (4) Measurement results: The above-mentioned coated fish fillets were refrigerated for 18 days and taken out to measure relevant indicators. The volatile basic nitrogen (TVB-N) was 16.86mg/100g, the total number of colonies (TVC) was 10 5.63 CFU/g, and the sulfide The barbituric acid value (TBA) is 0.63mg/kg, and the pH is 6.78. Fish fillets also have high edible value.

实施例2 Example 2

(1)保鲜涂膜的制备:用天平分别称取2.0g胶原蛋白和0.6g壳聚糖溶解于100mL的pH 4.0水溶液中,混合均匀后将混合液在圆底烧瓶中于80℃回流反应8小时得到美拉德反应产物。将美拉德反应产物倒入烧杯中,冷却到室温,加入6mL甘油搅拌均匀,超声8分钟脱除气泡,得保鲜涂膜。 (1) Preparation of fresh-keeping coating film: Weigh 2.0g collagen and 0.6g chitosan with a balance and dissolve them in 100mL of pH 4.0 aqueous solution. hours to obtain the Maillard reaction product. Pour the Maillard reaction product into a beaker, cool to room temperature, add 6 mL of glycerin, stir evenly, and ultrasonically remove air bubbles for 8 minutes to obtain a fresh-keeping coating.

(2)实施涂膜:将鲜活罗非鱼去鳞,去内脏,洗干净,切片,放入上述保鲜涂膜浸渍2分钟,取出沥干1分钟,这时鱼片表面形成一层保鲜薄膜。 (2) Coating: remove the scales and viscera of the fresh tilapia, wash it, slice it, put it in the above-mentioned fresh-keeping coating film for 2 minutes, take it out and drain it for 1 minute, at this time a layer of fresh-keeping film is formed on the surface of the fish fillet .

(3)冷藏处理:取冷却到室温的已高温高压灭菌的培养皿两个,一大一小,将上述涂好膜的鱼片放入小的培养皿中,再用大的培养皿将小的盖好,一起放入4℃的冰箱中冷藏。 (3) Refrigeration treatment: Take two high-temperature and high-pressure sterilized petri dishes that have been cooled to room temperature, one large and one small, put the above-mentioned fish fillets coated with the film into the small petri dishes, and then use the large petri dish Cover the small ones and put them together in the refrigerator at 4°C.

(4)测定结果:上述涂膜鱼片冷藏16天后取出测定相关指标,其挥发性盐基氮(TVB-N)为17.28mg/100g,菌落总数(TVC)为105.71 CFU/g,硫代巴比妥酸值(TBA)为0.67mg/kg,pH为6.84,鱼片还具有较高的食用价值。 (4) Measurement results: The above-mentioned coated fish fillets were refrigerated for 16 days and then taken out to measure relevant indicators. The volatile base nitrogen (TVB-N) was 17.28mg/100g, the total bacterial colony (TVC) was 10 5.71 CFU/g, and the sulfide The barbituric acid value (TBA) is 0.67mg/kg, the pH is 6.84, and the fish fillet also has a high edible value.

实施例3 Example 3

(1)保鲜涂膜的制备:用天平分别称取1.3g胶原蛋白和1.3g壳聚糖溶解于100mL的pH 5.0水溶液中,混合均匀后将混合液在圆底烧瓶中于90℃回流反应9小时得到美拉德反应产物。将美拉德反应产物倒入烧杯中,冷却到室温,加入8mL甘油搅拌均匀,超声5分钟脱除气泡,得保鲜涂膜。 (1) Preparation of fresh-keeping coating film: Weigh 1.3g collagen and 1.3g chitosan with a balance and dissolve them in 100mL of pH 5.0 aqueous solution, mix well and then reflux the mixture in a round bottom flask at 90°C hours to obtain the Maillard reaction product. Pour the Maillard reaction product into a beaker, cool to room temperature, add 8 mL of glycerin, stir evenly, and ultrasonically remove air bubbles for 5 minutes to obtain a fresh-keeping coating.

(2)实施涂膜:将鲜活罗非鱼去鳞,去内脏,洗干净,切片,放入上述保鲜涂膜浸渍2分钟,取出沥干1分钟,这时鱼片表面形成一层保鲜薄膜。 (2) Coating: remove the scales and viscera of the fresh tilapia, wash it, slice it, put it in the above-mentioned fresh-keeping coating film for 2 minutes, take it out and drain it for 1 minute, at this time a layer of fresh-keeping film is formed on the surface of the fish fillet .

(3)冷藏处理:取冷却到室温的已高温高压灭菌的培养皿两个,一大一小,将上述涂好膜的鱼片放入小的培养皿中,再用大的培养皿将小的盖好,一起放入4℃的冰箱中冷藏。 (3) Refrigeration treatment: Take two high-temperature and high-pressure sterilized petri dishes that have been cooled to room temperature, one large and one small, put the above-mentioned fish fillets coated with the film into the small petri dishes, and then use the large petri dish Cover the small ones and put them together in the refrigerator at 4°C.

(4)测定结果:上述涂膜鱼片冷藏18天后取出测定相关指标,其挥发性盐基氮(TVB-N)为16.98mg/100g,菌落总数(TVC)为105.65 CFU/g,硫代巴比妥酸值(TBA)为0.60mg/kg,pH为6.73,鱼片还具有较高的食用价值。 (4) Measurement results: The above-mentioned coated fish fillets were refrigerated for 18 days and taken out to measure relevant indicators. The volatile base nitrogen (TVB-N) was 16.98mg/100g, the total number of colonies (TVC) was 10 5.65 CFU/g, and the sulfide The barbituric acid value (TBA) is 0.60mg/kg, the pH is 6.73, and the fish fillet also has a high edible value.

Claims (6)

1. collagen protein and chitosan are prepared a method for fresh-keeping film-coating by Maillard reaction, it is characterized in that comprising the following steps:
(1) collagen protein and chitosan are dissolved in acidic aqueous solution, in round-bottomed flask, 80 ~ 100 ℃ of back flow reaction are 8 ~ 10 hours, obtain maillard reaction product;
(2) above-mentioned maillard reaction product is cooled to 20-25 ℃, adds glycerine to stir, ultrasonic 3-8 minute removes bubble, obtains described fresh-keeping film-coating.
2. preparation method according to claim 1, is characterized in that: in described step (1), the pH of the acidic aqueous solution of described dissolving collagen protein and chitosan is 4.0 ~ 6.0.
3. preparation method according to claim 1, is characterized in that: in described step (1), the concentration of collagen protein is 0.006 ~ 0.02g/mL.
4. preparation method according to claim 1, is characterized in that: in described step (1), the concentration of chitosan is 0.006 ~ 0.02g/mL.
5. preparation method according to claim 1, is characterized in that: in described step (2), glycerine consumption is 6 ~ 10mL/100mL.
6. the fresh-keeping film-coating of the preparation of method, for oppressing fresh-keeping method, is characterized in that according to claim 1: the flesh of fish is put into described fresh-keeping film-coating and flood, drain, on the surface of the flesh of fish, form one deck antistaling film.
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